1-Substituted-1,2,4-triazoles

ABSTRACT

in which X1 represents hydrogen or an alkyl radical, X2 represents hydrogen or an alkyl radical, R1 represents an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or optionally substituted aryl or aralkyl radical, R2 represents hydrogen or an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or optionally substituted aryl or aralkyl radical, R3 represents hydrogen or an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or optionally substituted aryl or aralkyl radical, and Y represents a keto group or a functional keto derivative, WHICH POSSESS FUNGICIDAL PROPERTIES. 1-SUBSTITUTED-1,2,4-TRIAZOLES OF THE FORMULA

United States Patent [191 Meiser et al.

[451 Oct. 14, 1975 II-SUBSTITUTED-LZA-TRIAZOLES [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen, Germany 22 Filed: Dec. 27, 1972 21 "Appl. No.: 318,963

[30] Foreign Application Priority Data Jan. 11, 1972 Germany 2201063 [52] US. Cl. 260/308 R; 424/269 [51] Int. Cl. C07D 249/08 [58] Field of Search 260/308 R Primary ExaminerNorma S. Milestone Assistant Examiner-Robert T. Bond Attorney, Agent, or Firm-Burgess, Dinklage & Sprung [57] ABSTRACT l-substituted-l,2,4-triazoles of the formula in which X represents hydrogen or an alkyl radical,

X represents hydrogen or an alkyl radical,

R represents an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or optionally substituted aryl or aralkyl radical,

R represents hydrogen or an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or optionally substituted aryl or aralkyl radical,

R represents hydrogen or an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or optionally substituted aryl or aralkyl radical, and

Y represents a keto group or a functional keto derivative,

which possess fungicidal properties.

7 Claims, No Drawings lSUBSTITUTED-1,2,4-TRIAZOLES.

The present invention relates to and has for its objects the provision of particular new l-substituted 1,2,4-triazoles, i.e. l-[l',2',4'-(optionally 2',5'- substituted)triazolyl-( l 1-alkoxyor -aroxybutanones and ketals thereof, as well as salts thereof, which possess fungicidal properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating pests, e. g. fungi, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

It is known from US. Pat. No. 2,425,341 that ndodecylguanidine acetate (Compound A) possesses fungicidal activity, both protective and curative. Since the toleration of this compound by some types of fruit is low, however, it can only be used preceding blossoming.

It is also known from Swiss Patent Specification No. 488,713 that l-trityl-l,2,4-triazole (Compound B) is fungicidally active. However, its action is not always entirely satisfactory if low amounts and concentrations are used.

The present invention provides compounds which are 1,2,4-triazole derivatives or salts thereof, the 1,2,4- triazole derivatives being of the general formula in which X represents hydrogen or an alkyl radical,

X represents hydrogen or an alkyl radical,

R represents an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or optionally substituted aryl or aral-, kyl radical,

R represents hydrogen or an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or optionally substituted aryl or aralkyl radical,

R represents hydrogen or an alkyl, alkenyl, alkynyl,

cycloalkyl, cycloalkenyl or optionally substituted aryl or aralkyl radical, and

Y represents a keto group or a functional keto derivative.

Surprisingly, the compounds according to the invention show a considerably higher fungicidal action than the n-dodecyl-guanidine acetate and l-trityl-l ,2,4- triazole known from the prior art, which are the nearest active compounds of similar mode of action. The substances according to the invention thus represent an enrichment of the art.

In formula I hereinabove X and X can be the same or different and preferably represent hydrogen or a straight-chain or branched loweralkyl radical with l to 3 carbon atoms, especially methyl.

R preferably represents a straight-chain or branched alkyl radical with l to 8, especially 1 to 4, carbon atoms, a straight-chain or branched alkenyl radical with 2 to 6, especially 3 to 6, carbon atoms, a straightchain or branched alkynyl radical with 2 to 6, especially 3 to 6, carbonatoms, a cycloalkyl or cycloalkenyl radical with 5 to 7, especially 5 or 6, carbon atoms, an optionally substituted aryl radical with 6 to 10 carbon atoms or an optionally substituted aralkyl radical with 6 to 10 carbon atoms in the aryl moiety and l or 2 carbon atoms in the alkyl moiety. Preferered substituents of the two last-mentioned radicals include: halogen, especially fluorine, chlorine or bromine, nitro, straightchain or branched alkyl with l to 6, especially 1 to 4, carbon atoms, alkoxy with l to 4, especially 1 or 2, carbon atoms, alkylthio with l to 4, especially 1 or 2, carbon atoms, haloalkyl with l or 2 carbon atoms and 1 to 5 halogen atoms, especially fluorine or chlorine, haloalkylthio with l or 2 carbon atoms and 3 to 5 halogen atoms (for example difluorochloromethyl), haloalkylsulfonyl with l or 2 carbon atoms and l halogen atom, especially chlorine, (for example chloromethylsulfonyl), or 0- or p-linked phenyl.

R preferably represents hydrogen, a straight-chain or branched alkyl radical with l to 6, especially 1 to 4, carbon atoms, a straight-chain or branched alkenyl radical with 2 to 6, especially 2 to 4, carbon atoms, a straight-chain or branched alkynyl radical with 2 to 6, especially 2 to 4, carbon atoms, a cycloalkyl or cycloalkenyl radical with 5 to 7, especially 5 or 6, carbon atoms, an optionally substituted aryl radical with 6 to 10 carbon atoms or an optionally substituted aralkyl radical with 6 to 10 carbon atoms in the aryl moiety and l or 2 carbon atoms in the alkyl moiety (for example phenyl or benzyl). Preferred substituents of the aryl or aralkyl radicals include: halogen, especially fluorine, chlorine or bromine, straight-chain or branched alkyl with l to 4 carbon atoms or haloalkyl with 1 or 2 carbon atoms and 2 to 5 halogen atoms, especially fluorine or chlorine.

R preferably represents any of the radicals mentioned under R.

Y preferably represents a carbonyl group, which can optionally be present in the hydrated form C- (OH or a ketal group C(OR) wherein R represents an alkyl radical, preferably with l or 2 carbon atoms.

The invention also provides a process for the production of a compound as defined above in which a. a haloether-ketone of the general formula in which R, R R and Y have the abovementioned meanings,

and Hal represents halogen, especially chlorine or bromine, is reacted with a 1,2,4-triazole of the general formula (III) in which Y X and X have the abovementioned meanings, op-

tionally in the presence of an acid-binding agent and optionally in the presence of a diluent, or b. a hydroxy-ether-ketone of the general formula R-OCYR-" in which R, R and R have the abovementioned meanings, is reacted with a 1,2,4-triazole of the formula (III), optionally in the presence of a diluent and optionally in the presence of a dehydrating agent, or

c. a hydroxy-ether-ketone of the formula (IV) is reacted with a compound of the general formula Nl [N- in which Z represents the S or CO group, optionally in the presence of a diluent, or d. a compound of the general formula in which R, R and R have the abovementioned meanings, is

reacted with a 1,2,4-triazole hydrochloride of the general formula I (VII) fi Q-O-CH-CO-Q E JN T (11a) (IIIa) 4 If [1-hydroxy1-[l -(2,4'-dichloro )-phenoxy]-3 ,3- dimethylbutan-Z-one and l,2,4 -triazole are used as the starting substances in process variant (b), the course of the reaction can be represented by the following equation:

CI (I) If [1-hydroxy]-[1 (2,4-dichloro)-phenoxy]-3 ,3- dimethylbutan-Z-one and thionyl-bis-l,2,4-triazole are used as starting substances in process variant (0), the

course of the reaction can be represented by the following equation:

dimethylbutan-Z-one and 1,2,4-triaz'ole hydrochloride are used as the starting substances in process variant (d), the course of the reaction can be represented by the following equation:

N 1 l l 01 N I VIII Q g o methylphenoxy)-acetophenone,

l ClQO-LEL/T-MCH,

dichlorophenoxy )-3 ,3-dimethyl-butan-2-one, l-

bromo- I 2 ',5 -dichlorophenoxy)-3 ,3-dimethyl-butan- 30 2-one, l-bromol 4'-methoxyphenoxy )-3,3-dimethylbutan-2-one, 1-bromo-l-(2'-methylphenoxy)-3,3- dimethyl-butan-Z-one, l-bromo-l-(2',3'-

. dichlorophenoxy)-3,3-dimethyl-butan-2-one, l-bromol-(4-bromophenoxy)-3 ,3-dimethyl-butan-2-one, 1- bromo-1-(4-fluorophenoxy)-3,3-dimethyl-butan- 2-one, l-bromol 2 ',4',6-trichlorophenoxy)-3 ,3- dimethyl-butan-Z-one, l -bromo-1 -(4-tert.-butylphenoxy)-3,3-dimethyl-butan-2-one, l-bromo-1-(4'- isopropyl-phenoxy)-3,B-dimethyLbutan-Z-one, bromo-1-(2' -methyl-4'-chlorophenoxy)-3,3-dimethylbutan-Z-one, l-bromo-l-(4'-trifluoromethylphenoxy)- 3,3-dimethyl-butan-2-one, 1-bromo-1-(4' nitrophenoxy)-3,3-dimethyl-butan-2-one, l-bromo-l- (2 -nitrophenoxy)-3 ,3-dimethyl-butan-2-one, lbromo-l-(p-diphenoxy)-3,3-dimethyl-butan-2-one, lbromo-l-(o-diphenoxy)-3,3-dimethyl-butan-2-one, w-bromo-w-phenoxy-acetophenone, w-brmo-w-(4'- chlorophenoxy)-acetophenone, w-bromo-w-( 3 chlorophenoxy)-acetophenone, m-br0m0-w-(2',4'- dichlorophenoxy)-acetophenone, w-br0mo-w-(4'- w-chloro-w-( 2 chloro-4-methyl-phenoxy)-acetophenone, m-chlorow-(2-methyl-4'-chloro-phenoxy)-acetophenone, w-bromo-w-(Z'-methyl-phenoxy)-acetophenone, m-chlorow-(2',4'-dichlorophenoxy)-4-chloroacetophenone, and w-bromo-w-(2,6'-dichlorophenoxy)-acetophone.

Many of the halogen compounds of the formula (II) used as starting substances are known, and those which are not yet known can be prepared according to known processes, for example by reacting a compound of the formula R -OH (Vlll) in which R has the meaning indicated above, with a haloketone of the formula CIQOH H Hal-(L-CO-Jl (IX) in which R and R have the abovementioned meanings, and

Hal represents halogen, preferably chlorine or bromine.

The active hydrogen atom which still remains may be subsequently replaced by halogen in the usual manner and the keto group is optionally converted into a functional derivative.

The following may be mentioned as examples of the 1,2,4-triazoles of the formula (III) which can be used according to the invention: l,2,4,-triazole, 3-methyl- 1,2,4-triazole and 3,5-dimethyl-l,2,4-triazole. These compounds are known.

The following may be mentioned as examples of the compounds of the formula (IV) which can be used according to the invention: w-hydroxy-w-methyl-wphenoxy-acetophenone, m-hydroxy-w-methyl-m-(4- chlorophenoxy)-acetophenone, m-hydroxy-w-methylw-(2',4'-dichlorophenoxy)-acetophenone, m-hydroxyw-phenoxy-acetophenone, w-hydroxy-w-(4'- chlorophenoxy)acetophenone, w-hydroxy-w-(2',4'- dichlorophenoxy)-acetophenone, w-hydroxy-w-( 3 chlorophenoxy)-acetophenone, w-hydroxy-w-( 2 chlorophenoxy)-acetophenone, w-hydroxy-m-(2',5- dichlorophenoxy)-acetophenone, w-hydroxy-m-(2 ,6 dichlorophenoxy)-acetophenone, w-hydroxy-w-(4'- fluorophenoxy )-acetophenone, w-hydroxy-w-( 4 bromophenoxy )-acetophenone, w-hydroxy-w-( 4 methylphenoxy)-acetophenone, l-hydroxyl -phenoxy- 3 ,3 -dimethyl-butan-2-one, l -hydroxy-1-(4'- chlorophenoxy)-3,3-dimethyl-butan-2-one, l-hydroxy- 1-(2',4'-dichlorophenoxy)-3 ,3-dimethyl-butan-2-one, l-hydroxy- 1 2',6'-dichlorophenoxy)-3 ,3-dimethylbutan-2-one and l-hydroxy-l-(2',5 dichlorophenoxy)-3,3-dimethyl-butan-2-one.

The compounds of the formula (IV) can be prepared from the halogen derivatives of the formula (II) in the usual manner or in accordance with known processes, for example by the reaction of a-B-diketones or a-ketoaldehydes with alcohols in accordance with the following equation, with R, R and R in the formulae having the meanings indicated above:

The keto group of the ketones thus produced can optionally be converted into functional derivatives in accordance with customary methods.

The thionylor carbonyl-bis-l,2,4-triazoles used as starting substances for process variant have the formula (V); they have hitherto been unknown but can be readily prepared according to known processes, e.g. Angew. Chem. 68, page 754 (1956).

The starting substances for the process variant (d) are generally defined by the formula (VI). In this case i R can preferably represent hydrogen as well as any of the preferred radicals mentioned above in connection with R The following may be mentioned as examples of the compounds of the formula (IV) which can be used according to the invention: l-phenyl-l,l-bis-phenoxy- 3,3-dimethyl-butan-2-one,

chlorophenoxy)-acetophenone, 2-dimethoxy-butan-3; -one, 2-diethoxy-butan-3-one, 2-bis-phenoxy-butan-f 3-one, Z-dimethoxy-ethan-Z-one, a,a-bis-methylbenzil-ketal, a,a-bis-ethyl-benzil-ketal, 1,1-dimethoxyl,2-bis-cyclohexyl-ethan-2-one, l,l-dimethoxy-1,2-biscyclopentyl-ethan-2-one, 2,5-dimethyl-3,3-dimethoxyhexan-4-one, 2,5-dimethyl-3,3-diethoxy-hexan-4-one and 2,5-dimethyl-3,3-bis-phenoxy-hexan-4-one.

Many of the ketals used as starting substances of the 5 formula (VI) are known. Those which are not yet known can be prepared according to customary processes, e.g. .l. Chem. Soc. (London) (1970) 3, 462464. Liebigs Ann. Chem. 735 (1970) 145-157. 'These ketals can furthermore be prepared by Reformatzky synthesis or Grignard synthesis which leads to an aralkyl-ketone, and also by bromination on the carbon atom adjacent to the keto group and by reaction of the resulting dibromo-ketone with an alcoholate or phenolate, in accordance with the following two equations:

Equation XVI:

2 NaBr Equation XVll:

- 2 NaBr The compounds of formula (VII) may for example be the hydrochlorides of any of the compounds of formula (III) specified herein. I

The preferred salts of the 1,2,4-triazole derivatives of the formula (I) are those with physiologically tolerated acids. Examples of such acids are the hydrogen halide acids, for example hydrobromic acid and, especially, hydrochloric acid, phosphoric acid, monofunctional and bifunctional carboxylic acids and hydroxycarboxylic acids. for example acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid, lactic acid, and 1,5-naphthalenedisulfonic acid.

Preferred diluents for process variant (a), involving reaction of the halogen derivatives of the formula (II) with l,2,4-triazoles of the formula (III), are polar organic solvents. Preferred examples include nitriles, such as acetonitrile; sulfoxides, such as dimethylsulfoxide; formamides, such asdimethylformamide; ke-

tones, such as acetone; ethers, such as diethyl-ether or tetrahydrofuran; nitroalkanes, such as nitromethane; and chlorinated hydrocarbons, such as methylene chloride and chloroform.

The reaction of variant (a) is preferably carried out in the presence of an acid-binding agent. Preferably, an appropriate excess of 1,2,4-triazole is used for this purpose. However, it is also possible to add any of the other organic acid-binding agents usually employed,

such as lower tertiary alkylamines or aralkylamines, for

example triethylamine or dimethylbenzylamine, it is also possible to add inorganic acidbinding agents, for example potassium carbonate.

In process variant (a) the reaction temperatures can be varied over a wide range. In general the reaction is carrier out at about 20 to 150C, preferably about 80C to 120C.

In carrying out process variant (a), it is preferred to use about 1 mole of 1,2,4-triazole and about 1 mole of acid-binding agent for each mole of the compound of the formula (II).

To isolate the produce of the formula (I), the solvent may be evaporated off in vacuo and the residue may be taken up in an organic solvent. This may be followed by extraction with water to remove the 1,2,4-triazolyl hydrochloride which is produced at the same time, and evaporation of the solution to dryness. The base may be isolated from the residue by recrystallization, and the salt by treatment with the appropriate acid in accordance with customary methods.

Possible diluents for process variant (b), involving reaction of the compounds of the formula (IV) with 1,2,4-triazoles of the formula (III), include all inert high-boiling organic solvents. Preferred examples include aromatic hydrocarbons, such as chlorobenzene. The water of reaction produced can be removed azeotropically by means of this solvent. Process variant (b) can also be carried out without solvents, forexample in the melt.

It may be appropriate, when carrying out process variant (b), to add a dehydrating agent, preferably an alkaline earth metal oxide, such as MgO, BaO, CaO or aluminium oxide, to facilitate the splitting off of water.

The reaction temperatures can be varied over a wide range in process variant (b). In general, the reaction is carried out at about 100 to 230C, preferably about l40to 200C and especially about 170 to 190C. If a solvent is present, the reaction may be appropriately carried out at the boiling point of the particular solvent.

When carrying out process variant (b), it is preferred to use 1 to 2 moles of 1,2,4-triazole, and 1 to 3 moles of dehydrating agent when employed, for each mole of the compound of the formula (IV). The products of the formula (I) may be isolated in accordance with customary methods.

Possible diluents in the process variant (c) involving reaction of compounds of the formula (IV) with compounds of the formula (V), include all inert organic solvents. Preferred examplesinclude aromatic hydrocarbons, such as benzene or toluene, ethers such as diethyl ether or tetrahydrofuran, chlorinated hydrocarbons, such as methylene chloride, chloroform or carbon tetrachloride, and lower alkyl nitriles, such as acetonitrile.

The reaction temperatures can be varied over a wide range in process variant (c). In general, the reaction is carried out at about to 120C, preferably about to 100C.

When carrying out the process variant (c), it is preferred to use about 1 mole of the compound of the formula (V) for each mole of the compound of the formula (IV). The products-of the formula (I) may be isolated in accordance with customary methods.

As diluents in the process variant (d) involving reaction of compounds of the formula V1) with 1,2,4-

triazole hydrochlorides of the formula (VII), it is possible to use high-boiling polar organic solvents. Preferred examples include sulfoxides, such as dimethylsufoxide,

formamides, such as dimethylformamide, and ethers,

such as dioxand or dibutyl ether. The reaction according to process variant (d) is, however, preferably car- I ried out without solvents, that is to say in the melt.

It can be appropriate to add an acid catalyst, for example hydrochloric acid or p-toluenesulfonic acid, when carrying out process variant (d), in order to facilitate the splitting off of alcohol or phenol.

The reaction temperatures can be varied over a wide range in process variant (d). In general, the reaction is carried out at about to 250C, preferably to 200C, especially to C. If a solvent is used, the process is appropriately carried out at the boiling point of the particular solvent.

In carrying out the process variant (d), it is preferred to use about 1 mole of 1,2,4-triazole hydrochloride, and 0.01 to 0.1 mole of acid catalyst if used, for each mole of the compound of the formula (VI).

To isolate the products of the formula (I), the reaction mixture may be taken up in water, whereupon it partly dissolves; the suspension may be neutralized with alkali or alkali carbonate and extracted with organic solvents which are slightly miscible with water, for example methylene chloride. The organic phase may be dried and the solvent distilled off. The resulting solid or oily residue may be purified by recrystallization.

The compounds of the formula (I) obtained according to the process variants (a), (b), (c) or (d) can be converted into functional derivatives of the keto grouping and/or into their salts in accordance with the customary methods.

The following are examples of the new active compounds of the invention which can be prepared in accordance with the process of the invention: [lo-(1,2,4- triazolyl-l ]-[w-phenoxy]-acetophenone, [w-( 1,2,4- triazolyl-l -[m-4-chlorophenoxy] -acetophenone, m-( 1,2,4-triazolyl-1')]-[w-3 '-chlorophenoxy]- acetophenone, [w-(1,2,4-triazolyl-1')]-[m-2,4'- dichlorophenoxy]-acetophenone, [w-( 1,2,4-triazolyl- 1 )]-[m-2',4 '-dichlorophenoxy]-4- chloroacetophenone, [w-( 1,2,4-triazolyl-1 ]-[w-2',6'- dichlorophenoxy]-acetophenone, [w-( 1,2,4-triazolyl- 1 ]-[w-4'-methoxyphenoxy]-acetophenone, [w- 1,2,4-triazolyl-1 ]-[co-4'-methylphenoxy]- acetophenone, [w-( 1,2,4-triazolyl-l ')]-[m-2'-methylphenoxyl-acetophenone, [w-methyl]-[m-( 1,2,4- triazolyl-l )]-[w-4-chlorophenoxy]-acetophenone, m-phenyl]-[w-( 1,2,4-triazolyl-I )]-[to-2',4'-dichlorophenoxyl-acetophenone, [2-( 1,2,4-triazolyI-1 2- (2 ',4'-dichlorophenoXy ]-acetaldehyde, 1-( 1,2,4- triazolyl-l H l-( 2',4'-dichlorophenoxy ]-propan- 2-one, [2-(l,2,4-triazolyl-1')]-[2-phenoxy]-butan- 3-one, [2-(1,2,4-triazolyl 1')]-[2-(4-chlorophenoxy)]-butan-3-one, [2-(1,2,4-triazolyl-l')]-[2-(4-fluorophenoxyl-butan-3-one, [2-( l,2,4-triazolyl-1')]-[2- (2,4'-dichlorophenoxy]-butan-3-one, [l-( 1,2,4- triazolyl-l l-(2',4'-dichlorophenoxy)]-3-methylbutan-2-one, [2-(1,2,4-triazolyl-1')]-[2-(4'- chlorophenoxy) ]-4-methyl-pentan-3-one, [2-( l ,2,4- triazolyl- 1 H 2 2,4'-dichlorophenoxy)]-4-methylpentan-3-one, [1-( 1,2,4-triazolyl- 1 ')]-[1-(4'- chlorophenoxy)]-3,3-dimethyl-butan-2-one, [l-(1,2,4- triazolyl-l l-( 2,4'-dichlorophenoxy)]-3,3- dimethyl-butan-Z-one, l-( 1,2,4-triazolyl-l l- (2 ,5 '-dichlorophen0Xy) ]-3,3-dimethyl-butan-2-one, [1-( 1 ,2,4-triazolyl-l l-(2',6'- dichlorophenoxy)] 1 3 ,3-dimethyl-butan-2-one, 1- (l,2,4-triazolyl-l)]-[1-(2,4',6'-trichlorophenoxy)]- 3,3-dimethyl-butan-2-one, [l-( 1,2,4-triazolyl-1')]-[ l- (2-chlorophenoxy)]-3,3-dimethyl-butan-2-one, l- (1,2,4-triazolyl-1')]-[l-(4-bromophenoxy)]-3,3- dimethyl-butan-Z-one, [1-( 1 ,2,4-triazolyl-l l-(4- fluorophenoxy)]-3,3-dimethyl-butan-2-one, [l-( l ,2,4- triazolyl-l l-(4'-methylphenoxy)]-3 ,3-dimethylbutan-2-one, [1-( 1,2,4-triazolyl-1)]-[ 1-( 4'- methoxyphenoxy -3 ,3-dimethyl-butan-2-one, ll,2,4-triazolyl-4)]-[ l-(4'-tert.-butylphenoxy)]-3,3- dimethyl-butan-Z-One, 1-( 1 ,2,4-triazolyl-l l-(4'- isopropylphenoxy) 1-3 ,3-dimethyl-butan-2-one, l- 1,2,4-triazolyl-l l-(2-methyl-4- chlorophenoxy)1-3,3-dimethyl-butan-2-one, [1-( l ,2,4- triazolyl-l l-(4-trifluoromethylphenoxy)]-3,3- dimethyl-butan-2-one, [l-(1,2,4-triazolyl-1)]-[l-(4'- nitrophenOXy)]-3 ,3-dimethyl-butane-2-one, l-( l ,2,4- triazolyl-1')]-[ l-(2'-nitrophenoxy)]-3,3-dimethylbutan-2-one, [1-( 1,2,4-triazolyl-l l-(40'- fluorodichloromethylmercaptophenoxy)]-3,3- dimethyl-butan-Z-one, [1-( l ,2,4-triazolyl-l l-(4'- chloromethylsulphonyl-phenoxy)1-3 ,3-dimethylbutan-2-one, [1-(1,2,4-triazolyl-l)]-[1-(pdiphenoxy) ]-3,3-dimethyl-butan-2-one, [1-( 1,2,4 -triazolyl-l l-(o-diphenoxy)]-3,3-dimethyl-butan- 2-one, [2-( 1 ,2,4-triazolyl-l )]-[2-phenoxy]-4-dimethyl-pentan-3-one, [2-(1,2,4-triazolyl-l)]-[2-(4- fluorophenoxy) ]-4-dimethyl-pentan-3-one, [2-( 1,2,4- triazolyl-l ]-[2-( 2 ',4'-dichlorophenoxy -4-dimethylpentan-3-one, [l-phenyl]-[ l-(1,2,4-triazolyl-l)]-[lphenoxy]-3,3-dimethyl-butan-2-one, [l-phenyl]-[ 1- (1,2,4-triazolyl-l l-(4'-fluorophenoxy)]-3,3- dimethyl-butan-Z-one, [l-phenyl]-[ 1-( 1,2,4-triazolyll H l-( 2',4'-dichlorophenoxy)]-3,3-dimethyl-butan- 2-one, [2-( l ,2,4-triazolyl-1)]-[2-(2',4- dichlorophenoxy)]-l-cyclohexyl-ethan-l-one, [2- (1,2,4-triazolyl-l )]-[2-(2,4-dichlorophenoxy)]-1- cyclopentyl-ethan-l-one, and [2-(l,2,4-triazolyl-1')]- [2-( 2 ',4'-dichlorophenoxy) ]-3-cyclohexyl-propan- 3-one, as well as their salts, for example the hydrochlorides.

As particularly active compounds there may be mentioned: l-(1,2,4-triazolyl-1')]-[1-(4- chlorophenoxy)]-3,3-dimethyl-butan-2-one and its hydrochloride, and l-( 1,2,4-triazolyl-l l-(2',4- dichlorophenoxy)1-3,3-dimethyl-butan-2-one and its hydrochloride.

The active compounds according to the invention display a strong fungitoxic action. They do not appear to damage crop plants at the concentrations necessary for combating fungi and are of low toxicity to warmblooded animals. For these reasons they are suitable for use as plant protection agents for combating fungi. Fungitoxic agents are employed in plant protection for combating Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes and Fungi Imperfecti. The active compounds according to the invention have a very broad spectrum of action and can be used against parasitary fungi which infect above-ground parts of the plants or which attach plants through the soil, and against seed-borne pathogens.

They display a particularly good activity against parasitary fungi on above-ground parts of plants, such as species of Erysiphe and species of Venturia, and also against species of P ir icularia and Pellicularia, for example against the pathogens responsible for powdery mildew of apple (Podosphaera leucotricha), apple scab (Fusicladium dendriticum) and bunt of wheat (Tilletia tritici). It is to be emphasized that the active compounds according to the invention not only display a protective action but also are active curatively, that is to say when used after contamination with the spores of the fungus. Furthermore, attention should be drawn to the systemic action of the substances. Thus it is possible to protect plants against fungal attack if the active compound is supplied to the above-ground parts of the plant via the soil and the root. As plant protection agents, the substances according to the invention can be used for soil treatment, for seed treatment and for the treatment of aboveground parts of plants.

The substances according to the invention show good toleration by plants. They possess only slight toxicity towards warm-blooded animals and because of their slight odor and their good toleration by human skin they are not unpleasant to handle.

The active compounds according to the instant in- ,vention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pessticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. "The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), cycloalkanes (e.g. cyclohexane, etc.), paraffins (e.g. petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethers and esters thereof (e.g. glycol monomethyl ether, etc.), amines (e.g. ethanolamine, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.) acetonitrile, ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates. etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and- /or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, albumin hydrolyzates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate,

etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other fungicides or insecticides, acaricides, rodenticides, bactericides, nematocides, herbicides, fertilizers, bird repellents, growthenhancing compounds, growth-regulating agents, agents for improving soil structure, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

The formulations in general contain from 1 to 95 percent by weight of active compound, preferably 5 to 90 percent.

When used as leaf fungicides, the concentrations of active compound in the compositions applied can be varied over a wide range. They are generally from 0.1 to 0.00001 percent by weight, preferably 0.05 to 0.0001.

In the dressing of seed, amounts of active compound of 0.01 to 50 g per kilogram of seed, preferably 0.01 to 5 g, are in general required.

For soil treatment, amounts of active compound of l to 1,000 g per cubic meter of soil, preferably to 200 g, are in general required.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50-100 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about to 1000 g/hectare, preferably 40 to 600 g/hectare, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about to about 95% by weight of the active compound or even the 100% active. substance alone, e.g. about 20100% by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. fungi, which comprises applying to at least one of correspondingly (a) such fungi, and (b) the corresponding habitat thereof, i.e. the locus to be protected, a correspondingly combative or toxic amount, i.e. a fungicidally effective amount, of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The synthesis, unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without limitation, by the following examples:

EXAMPLE 1 Erysiphe Test Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether Water: parts by weight The amount of the active compound required for the desired concentration of active compound in the spray liquid was mixed with the stated amount of the solvent, and the concentrate was diluted with the stated amount of water containing the stated additions.

Young cucumber plants with about three foliage leaves were sprayed with the spray liquid until dripping wet. The cucumber plants remained in a greenhouse for 24 hours to dry. They were then, for the purpose of inoculation, dusted with conidia of the fungus Erysiphe cichoracearum. The plants were subsequently placed in a greenhouse at 23-24C and at a relative atmosphere humidity of about 75%.

After 12 days, the infection of the cucumber plants was determined as a percentage of the untreated but also inoculated control plants. 0% means no infection; that the infection was exactly was great as in the case of the control plants.

The active compounds, the concentrations of the active compounds and the results can be seen from the following Table 1.

Table I Active Compound Erysiphe Test Infection in of the infection of the untreated control at an active compound concentration of (known) (A) Podosphaera Test (powdery mildew of apples) [Protective] Table 1Continued Erysiphe Test Active Compound Infection in 7: of the infection of the untreated control at an active compound concentration of 0.00019% 0.00009% CH 7 01-6 OTHC0CCH;, (2 19 25 N Ha l N fl cl-i Cl O(\l-lCOC-Cll (1) I6 37 N CH 3 CI if N EXAMPLE 2 plants remained in a greenhouse for 24 hours at 20C and at a relative atmospheric humidity of They were then inoculated by dusting with conidia of the applepowdery mildew causative organism (Podosphaera leucotr icha Salm.) and placed in a greenhouse at a temperature of 2l-23C and at a relative atmospheric humidity of about 70%.

Ten days after the inoculation, the infection of the seedlings was determined as a percentage of the untreated but also inoculated control plants.

0% means no infection; means that the infection was exactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds and the results can be seen from the following Table 2;

Table 2 Active Compound Podosphaera Test Protective Infection in of the infection of the untreated control at an active compound concentration EXAMPLE 3 Fusicladium Test (Apple Scab) (Protective) Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether Water: 93 parts by weight The amount of active compound required for the desired concentrations of the active compound in the spray liquid was mixed with the stated amount of solvent, and the concentrate was diluted with the stated amount of water which contained the stated additions.

Young apple seedlings in the 4-6 leaf stage were sprayed with the spray liquid until dripping wet. The plants remained in a greenhouse for 24 hours at 20C and at a relative atmospheric humidity of 70%. They were then inoculated with an aqueous conidium suspension of the apple scab causative organism (Fusicladium dendriticum el) and incubated for 18 hours in a humidity chamber at l8-20C and at a relative atmospheric humidity of 100%.

The plants then again went into a greenhouse for 14 days.

15 days after inoculation, the infection of the seedlings was determined as a percentage of the untreated but also inoculated control plants.

means no infection; 100% means that the infection was exactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds and the results can be seen from the following Table 3:

Table 3 EXAMPLE 4 Fusicladium Test (Apple Scab) [Curative] Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether Water: parts by weight The amount of active compound required for the desired concentration of the active compound in the spray liquid was mixed with the stated amount of solvent, and the concentrate was diluted with the stated amount of water which contained the stated additions.

Young apple seedlings in the 4-6 leaf stage were inoculated with an aqueous conidium suspension of the apple scab causative organism (Fusicladium dendriticum el) and incubated for 18 hours in a humidity chamber at l8-20C and at an atmospheric humidity of The plants then went into a greenhouse where they dried.

After standing for a suitable period of time, the plants were sprayed dripping wet with the spray liquid prepared in the manner described above. The plants then again went into a greenhouse.

15 days after inoculation, the infectioin of the apple seedlings was determined as a percentage of the untreated but also inoculated control plants. 0% means no infection; 100% means that the infection was exactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds, the period of time between inoculation and spraying and the results can be seen from the following Table 4:

Infection in of the infection of the untreated control at an active compound concentration Table 4 Fusicladium Test Curative' Active compound Infection in 7! of Dwell time the infection of the unin hours treated control at an active compound concentration of 002571 C, H Nl-lC -CH CO0H 42 14 (known) (B) CH ci o n co c ci-i 42 0 v N .l

CH; Cl O(iHCOC CH 42 2 N\ 0 c] f N (1) EXAMPLE 5 greenhouse at 2324C and a relative atmospheric hu- Erysiphe Test/Systemic midity of 70%. After 12 days, the infection of the cucumber plants in per cent of the untreated but also inoculated control plants was determined.

0% denotes no infection and 100% denotes that the infection was exactly as high as in the case of the control plants.

The active compounds, active compound concentrations and results are shown in Table 5.

Table 5 Active Compound Erysiphe Test/Systemic lnfection in 7! of the infection of the untreated control at an active compound concentration of 30 ppm l5 ppm Cl I were inoculated with conidia of the fungus Erysiphe cichoracearum. Thereafter the plants were placed in a Fusicladium Test/Systemic Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether Water: parts by-weight The amount of active compound required for the desired concentration of the active compound in the watering liquid was mixed with the stated amount of solvent and the concentrate was diluted with the stated amount of water which contained the stated addition.

Apple seedlings grown in standard soil, in the 3-4 leaf stage, were watered once over the course of a week with 20 ml of the watering liquid in the indicated concentration of active compound, relative to 100 ml of soil.

The plants treated in this way were inoculated, after the treatment, with an aqueous conidium suspension of Fusicladium dentriticum el and incubated for 18 hours in a humidity chamber at 18-20C and at a relative atmospheric humidity of 100%. The plants then went into a greenhouse for 14 days.

15 days after inoculation, the infection of the seedlings was determined as a percentage of the untreated but also inoculated control plants. 0% means no infection; 100% means that the infection was exactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds and the results can be seen from the following Table 6.

Table 6 Table 7 Active Compound (known) (A) Fusicladiurn Test/Systemic Active Compound Infection in of the infection of the untreated control at an active compound concentration of ppm EXAMPLE 7 Pellicularia Test sprayed with the spray liquid until dripping wet. The

plants remained in a greenhouse at temperatures of 22 and 24C and a relative atmospheric humidity of about 70% until they had dried off. Thereafter the plants were infected with a culture of Pellicularia sasakii grown on malt agar and set up at 28 to 30C and 100% relative atmospheric humidity.

In the case of the plants infected with Pellicularia sasakii the infection was determined after 5-8 days on the leaf sheaths in relation to the untreated but infected control.

0% means no infection; 100% means that the infection was exactly as great as in the case of the control plants.

The active compounds, the concentrations of the active compounds and the results can be seen from the following Table 7.

CH N a Cl KINTN N J EXAMPLE 8 a. The starting material was prepared as follows:

35.8 g (0.2 mole) of a-bromo-pinacolone in ml of ethyl acetate were added dropwise to sodium 2,4- dichorophenolate which was prepared from 32.6 g (0.2

mole) of 2,4-dichlorophenol and 4.6 g (0.2 mole) of sodium in 130 ml of absolute alchol, and the mixture was heated to the boil over-night. Thereafter the sodium bromide produced was filtered off hot, the filtrate was distilled in vacuo and the solid residue was recrystallized from a little ligroin.

38 g (73% of theory) of 1-(2',4-dichlorophenoxy)- 3,3-dimethyl-butan-2-one of melting point 65C were obtained.

b. 6 ml (0.11 mole) of bromine were added to 26.1 g (0.1 mole) of l-(2,4-dichlorophenoxy)-3,3- dimethyl-butan-Z-one and the mixture was heated under reflux to 140C for 1 hour. The resulting oily residue was taken up with petroleum ether, whereupon it crystallized; the solid residue was filtered off and well rinsed.

g (89% of theory) of l-bromo-l-(2',4- dichlorophenoxy)-3,3-dimethyl-butan-2-one of melting point 70C were obtained.

CH c) c1 Q O--CH-CO-CCH3 (l) H U |/N\IN a 11.2 g (0.033 mole) of l-bromo-1-(2,4-

dichlorophenoxy-3,3-dimethyl-butan-2-one and 9.9 g (0.15 mole) of 1,2,4-triazole were dissolved in 80 ml of acetonitrile and heated under reflux for 48 hours. Thereafter the solvent was distilled off in vacuo, the residue was taken up with 150 ml of water and the aqueous solution was extracted by shaking three times with 40 ml of methylene chloride at a time. The organic phase was thereafter twice washed with 150 ml of water at a time, dried over sodium sulfate and distilled.

The oil obtained as residue was fractionally recrystallized from a little ether, whereby first 1 g of a product of melting point 145C, which was a by-product and was not identified, was obtained, followed by 7.6 g (70% of theory) of 1-[l,2,4-triazolyl-(l)]-l-[(2',4- dichloro)-phenoxy]-3,3-dimethyl-butan-2-one of melting point 65C.

d. Preparation of the hydrochloride:

phenoxyl]-3,3-dimethyl-butan-2-one were suspended in anhydrous ether and treated with a solution of hydrochloric acid in ether. Thereupon the material gradually dissolved. The ether was distilled off in vacuo. The

The resulting [l-l l,2 ,4-triazolyl-( l )]-l-(2',4'- 'dichlorophenoxy)-3-dimethyl'butan-2-onel hydrochloride had a melting point of 153C.

EXAMPLE 9 a. The starting material was prepared as follows:

6.5 g (0.2 mole) of 80% strength sodium hydride were suspended in 100 ml of anhydrous acetonitrile and 27 g (0.21 mole) of 4-chlorophenol in 50 ml of acetonitrile were added dropwise at room temperature while stirring and cooling.

After completion of the evolution of hydrogen, a further 27 g (0.105 mole) of l,l-dibromo-3,3-dimethylbutan-2-one (manufactured according to Organic Synthesis'lO, page 12) were added while stirring and cooling. Thereafter the mixture was slowly heated to the boil and boiled under reflux for 12 hours.

After cooling, the solvent was distilled off in vacuo, the residue was boiled up with hot ethyl acetate, active charcoal was added, the whole was filtered and again briefly boiled up and the solution was distilled initially in vacuo, and in a high vacuum after the solvent has distilled over.

54 g (76.5% of theory) of l,l-bis-(4-chlorophenoxy)-3,3-dimethyl-butan-2-one of boiling point b.p. 150C were obtained. The viscous oil solidified after some time.

panol.

17.7 g (0.05 mole) of l.l-bis-(4-chlorophenoxy)- 3,3-dimethyl-butan-2-one were intimately mixed with 5.9 g (0.055 mole) of 1,2,4-triazole hydrochloride and the mixture was heated to 220C over the course of 1 hour and left at this temperature for 30 minutes on doing so, the 4-chlorophenol split off commenced to boil.

After cooling, ml of 10% strength sodium hydroxide solution, covered withh 200 ml of ether, were added. The ether phase was separated off and washed three times with 30 ml of 5% strength sodium hydroxide solution at a time and twice with 50 ml of water at a time. After drying over sodium sulfate, the solvent was distilled off in vacuo. The oily residue was taken up in 100 ml of anhydrous ether and 0.055 mole of hydrogen chloride were passed into this solution. This produced a precipitate which after standing overnight was filtered off and rinsed with ether.

7.3 g (46% of theory) of l.-[l,2,4-triaZolyl-(1)]-l- (4'-chlorophenoxy)-3,3-dimethyl-butan-2-one hydrochloride of melting point 103-105C were obtained.

EXAMPLE usual manner and had a melting point of 58C.

18.0 g 0.05 mole) of w-bromo-w-(2',6'-dichlorophenoxy)-acetophenone and g (0.22 mole) of 1,2,4- triazole were dissolved in 120 ml of acetonitrile and the solution was heated under reflux for 48 hours. After distilling off the solvent in vacuo, the residue was taken up in 400 ml of water. This aqueous solution was extracted with methylene chloride as described and the organic phase was twice washed with 100 ml of water at a time and then dried over sodium sulfate, and the solvent was distilled off in vacuo. The oily residue obtained crystallized on heating with ether.

After recrystallization from ethylene chloride, 7 g (40% of theory) of w-[l,2,4-triazolyl-(l')]-w-[(2',6'- dichloro)-phenoxy]-acetophenone of melting point 166C were obtained.

EXAMPLE 1 1 a. l-bromol 4'-tert.-butyl )-phenoxy]-3 ,3- dimethyl-butan-Z-one (melting point 50C) used as the starting material was obtained by condensation of ptert.-butyl-phenol with a-bromopinacolone-(2) and subsequent bromination.

The residue was recrystallized from ligroin. 26 g (69% of theory) of l-[l,2,4-triazolyl-(l ')]-1-[(4'-tert.-

butyl)-phenoxy]-3,3-dimethyl-butan-2-one of melting point C were obtained.

EXAMPLE 12 a. The starting material was prepared as follows:

The Grignard compound was prepared from 38 g (0.3 mole) of benzyl chloride and 7.3 g (0.3 mole) of magnesium in 300 m1 of anhydrous ether. 21 g (0.25 mole) of pivalonitrile in 100 ml of anhydrous ether were added dropwise at the boil and the mixture was kept boiling under reflux for 3 hours.

After boiling, the reaction mixture was added to 1.5 liters of ice water, the ether phase was separated off and discarded and the aqueous phase was stirred for 2 hours on a waterbath. In the course thereof, the mixture gradually assumed an oily consistency. The oil was repeatedly extracted with 250 ml of methylene chloride and the organic phase was washed with water, dried and subjected to vacuum distillation.

40.5 g (92% of theory) of l-phenyl-3,3-dimethylbutan-2-one of boiling point b.p 8688C were obtained.

b. 17.6 g (0.1 mol) of l-phenyl-3,3-dimethyl-butan- 2-one were dissolved in 100 ml of carbon tetrachloride, 5 ml (0.1 mole) of bromine were added dropwise thereto while stirring and under reflux, and the mixture was heated to the boil for 1 hour. After cooling, and distilling off the solvent, 25.4 g of l-bromo-l-phenyl- 3,3-dimethyl-butan-2-one of melting point 3842C were obtained in quantitative yield.

c. A solution of 25.4 g (0.1 mole) of l-bromo-lphenyl-3,3-dimethyl-butan-2-one in 50 ml of ethyl acetate was added dropwise, at the boil, to a solution of 12.85 g (0.1 mole) of 4-chlorophenol and 2.3 g (0.1 mole) of sodium in 100 ml of ethanol. After boiling for 12 hours under reflux, the sodium bromide which had separated out was filtered off hot. The filtrate was distilled in vacuo and the solid residue which remained was recrystallized from ligroin. 20.2 g (67% of theory) of 1 -phenyll -(4'-chlorophenoxy )-3 ,3-dimethyl-butan- 2-one of melting point 103C were obtained.

, chloro-phenoxy)-3,3-dimethyl-butan-2-one were dissolved in ml of acetonitrile; thereafter 12 g (0.175

, solvent in vacuo. 200 ml of ice water were added. The

mixture was then extracted four times with 50 ml of methylene chloride at a time and the organic phase was 5 removed and washed three times with 50 ml of water at a time. It was dried and the solvent was distilled off in vacuo. The oily residue was recrystallized from lig- 5.3 g (29% of theory) of l-phenyl-l-(4-chlorophenoxy)-1-[ 1,2,4-tr'iazolyl-(l )]-3,3-dimethyl-butan- 2-one of melting point 130C were obtained.

EXAMPLE l3 The compounds listed below were prepared analogously. These compounds were all of formula (I) in which X and X and hydrogen and Y is CO, while the H C(CHQ:

roin. meanings of R, R and R are given in the table.

Com- R1 v R2 R Melting pound point. C

6 o H o 7 CIQ H 0 8 CIQ H Cl 101-104 9 Q- H C(CH3)3 110 Cl 10 Q H C(CH3)3 186 11 H C(CI- I10 12 BF-O- H C(CH,)3 89-92 13 H C(CH3);, boiling point 0.3 at 160C 14 cH,- H C(CHQ; so

15 CH(CH,)2 H C(CH=) 76 16' cl-Q H C(CH3)3 94-96 cH n o,N- H C(C a)a 129 I8 F c- H C(CH3)3 106 I9 Q0 IDS-I06 -Cntinued Com- R R R Melting pound boiling 36 CH H C(CHa), point 0.1/

' 145C CH (f.p. 7l)

37 Q- C(Cm) hydrochloride 38 Cl-Q- H C(CH3)3 75 39 Cl H CH3 hydrochloride cl I 40 H hydrochloride Cl 41 CI\Q H C(Cm)a 142-145 cl 42 Q H C(CI-n)a n4 43 Cl-Q- H C(CH 88-89 44 Cl- H C(CHQ; l0l

CH C1 45 Q H C CH 135-138 46 H C Cm) 74-75 47 Cl-Q- C(CH;,)3 hydrochloride It will be appreciated that the instant specification in which H and examples are set forth by way of illustration and X} and X each independently is hydrogen or alkyl of not limitation, and that various modifications and I 1 to 3 carbon atoms, changes may be made without departing from the spirit R is alkyl of 1 to 8 carbon atoms, alkenyl of 2 to 6 and scope of the present invention. carbon atoms, alkynyl of 2 to 6 carbon atoms, cy-

What is claimed is: cloalkyl of 5 to 7 carbon atoms, cycloalkenyl of 5 L A lzmmazole compound of the formula to 7 carbon atoms, or optionally substituted aryl of 6 to 10 carbon atoms or optionally substituted aral- 2 kyl of 6 to 10 carbon atoms in the aryl moiety and N l or 2 carbon atoms in the alkyl moiety, the op- X l N tional substituents being selected from the group I? consisting of halogen, nitro, alkyl of l to 6 carbon atoms, 'alkoxy of 1 to 4 carbon atoms, alkylthio of v l to 4 carbon atoms, haloalkyl of 1 to 2 carbon R atoms and l to 5 halogen atoms, haloalkylthio of l 33 34 to 2 carbon atoms and 3 to 5 halogen atoms, N haloalkylsulfonyl of l to 2 carbon atoms and l i halogen atom and or p-linked phenyl, N

R and R each independently is hydrogen, alkyl of l to 8 carbon atoms, alkenyl of 2 to 6 carbon atoms, 5 alkynyl of 2 to 6 carbon atoms, cycloalkyl of 5 to 7 carbon atoms, cycloalkenyl of 5 to 7 carbon atoms, or optionally substituted aryl of 6 to 10 carbon atoms or optionally substituted aralkyl of 6 to 10 carbon atoms in the aryl moiety and l to 2 car- 10 bon atoms in the alkyl moiety, the optional substituents being selected from the group consisting of halogen, nitro, alkyl of l to 6 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of l to 4 carbon atoms, haloalkyl of 1 or 2 carbon atoms and 1 to 5 halogen atoms, haloalkylthio of l or 2 carbon atoms and 3 to 5 halogen atoms, haloalkylsulfonyl of 1 or 2 carbon atoms and l halogen atom and 0- or p-linked phenyl, and

Y is -C(O), -C(OH) or C(OR) wherein R is methyl or ethyl,

or a salt thereof with a physiologically compatible acid.

2. A compound according to chaim 1 wherein X and X each is hydrogen or methyl,

R and R each independently is alkyl of l to 4 car- I II 5. The compound according to claim 1, wherein such compound is l-[ l,2,4-triazolyl-( l ')]-l-[4'-amino)- phenoxy]-3,3-dimethyl-butan-2-one of the formula bon atoms, alkenyl of 3 to 6 carbon atoms, alkynyl of 3 to 6 carbon atoms, cycloalkyl of 5 or 6 carbon atoms, cycloalkenyl of 5 or 6 carbon atoms, or op- H2N- -O-C-C0-C(CH,), tionally substituted aryl of 6m 10 carbon atoms, or

optionally substituted aralkyl of 6 to 10 carbon atoms in the aryl moiety and 1 or 2 carbon atoms in the alkyl moiety, the optional substituents being selected from the group consisting of fluorine, chlorine, bromine, nitro, alkyl of l to 4 carbon atoms, alkoxy of l to 4 carbon atoms, alkylthio of 1 or 2 carbon atoms, haloalkyl of 1 or 2 carbon atoms and l to 5 fluorine or chlorine atoms, haloalkylthio of l or 2 carbon atoms and 3 to 5 fluorine or chlorine atoms, monochloroalkylsulfonyl, and 0- or p-linked phenyl, and

R is hydrogen, alkyl of l to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms, alkynyl of 2 to 4 carbon atoms, cycloalkyl of 5 or 6 carbon atoms, cy-

cloalkenyl of 5 or 6 carbon atoms, or optionally substituted aryl of 6 to 10 carbon atoms or optionally substituted aralkyl of 6 to 10 carbon atoms in the aryl moiety and l or 2 carbon atoms in the alkyl moiety, the optional substituents being selected from the group consisting of fluorine, chlorine,

6. The compound according to claim 1 wherein such compound is 1-[ l ,2,4-triazolyl-( l )]-l-[(2',4- dichloro)-phenoxy]-3,3-dimethyl-butan-2-one of the formula 7. The compound according to claim 1 wherein such compound is l-phenyl-l-(4'-chloro-phenoxy)-l- 1,2,4-triazolyl-(1 ')]-3,3-dimethyl-butan-2-one of the formula bromine, alkyl of l to 4 carbon atoms and haloalkyl i H of 1 to 2 carbon atoms and 2 to 5 fluorine or chlo- Cl"O CC C(CH3)3 rine atoms.

3. The compound according to claim 1 wherein such 6 compound is l-[ l,2,4-triazolyl-( l')]-l-[(4'-nitro)- phenoxy1-3,3-dimethyl-butan-2-one of the formula PATENT NO.

DATED iN\/ ENTR(S) Page 1 of 2 October 14, 1975 WERNER MEISER ET AL Itis certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

ciQ o-cH-co-c(ca Patent Specification Col. Line Page Line 66 19 6 cancel "l3" and substitute 3 ll l7 19 20 cancel and substitute 4' 14 26 23 after "exactly" cancel 'was" and substitute as correct formula to read as follows:

UNITED STATES PATENT AND TRADEMARK OFFICE 4 CERTIFICATE OF CORRECTION PATENT 1 3,912,752 Page 2 of 2 DATED October 14, 1975 lNV ENTOR(S) WERNER MEISER ET AL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: 7 O

Patent Specification Col. Line Page Line 24 45 39 13 correct formula to read as follows:

c10- 0-(JH-CQ-O(CH3)3 x1101 I .1

24 5'8 39 22 correct spelling of. "with".

26 60 43 1, correct formula to read as follows: q

[I it I 9 Cl I I 0 t c Mon (5) v Engncd. and Scaled this I Twenty-fourth Day Of August 1976 [S I a v v Arrest: v

' mm! c.- msoN v i c MARSHALL D ANN '6" ff Commissioner of Patents and Trademarks 

1. A 1,2,4-TRIAZOLE COMPOUND OF THE FORMULA
 2. A compound according to chaim 1 wherein X1 and X2 each is hydrogen or methyl, R1 and R3 each independently is alkyl of 1 to 4 carbon atoms, alkenyl of 3 to 6 carbon atoms, alkynyl of 3 to 6 carbon atoms, cycloalkyl of 5 or 6 CARBON atoms, cycloalkenyl of 5 or 6 carbon atoms, or optionally substituted aryl of 6 to 10 carbon atoms, or optionally substituted aralkyl of 6 to 10 carbon atoms in the aryl moiety and 1 or 2 carbon atoms in the alkyl moiety, the optional substituents being selected from the group consisting of fluorine, chlorine, bromine, nitro, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 or 2 carbon atoms, haloalkyl of 1 or 2 carbon atoms and 1 to 5 fluorine or chlorine atoms, haloalkylthio of 1 or 2 carbon atoms and 3 to 5 fluorine or chlorine atoms, monochloroalkylsulfonyl, and o- or p-linked phenyl, and R2 is hydrogen, alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms, alkynyl of 2 to 4 carbon atoms, cycloalkyl of 5 or 6 carbon atoms, cycloalkenyl of 5 or 6 carbon atoms, or optionally substituted aryl of 6 to 10 carbon atoms or optionally substituted aralkyl of 6 to 10 carbon atoms in the aryl moiety and 1 or 2 carbon atoms in the alkyl moiety, the optional substituents being selected from the group consisting of fluorine, chlorine, bromine, alkyl of 1 to 4 carbon atoms and haloalkyl of 1 to 2 carbon atoms and 2 to 5 fluorine or chlorine atoms.
 3. The compound according to claim 1 wherein such compound is 1-(1,2,4-triazolyl-(1''))-1-((4''-nitro)-phenoxy)-3,3-dimethyl-butan-2-one of the formula
 4. The compound according to claim 1 wherein such compound is 1-(1,2,4-triazolyl-(1''))-1-((4''-chloro)-phenoxy)-3,3-dimethyl-butan-2-one of the formula
 5. The compound according to claim 1, wherein such compound is 1-(1,2,4-triazolyl-(1''))-1-(4''-amino)-phenoxy)-3,3-dimethyl-butan-2-one of the formula
 6. The compound according to claim 1 wherein such compound is 1-(1,2,4-triazolyl-(1''))-1-((2'',4''-dichloro)-phenoxy)-3,3-dimethyl-butan-2 -one of the formula
 7. The compound according to claim 1 wherein such compound is 1-phenyl-1-(4''-chloro-phenoxy)-1-(1,2,4-triazolyl-(1''))-3,3-dimethyl-butan-2-one of the formula 